Impact of Base Rubber and Cure Systems in Additive Manufacturing of Fully Compounded Thermoset Elastomers

While the effects of formulation variables of a rubber compound are well established for conventional rubber manufacturing techniques, their role in extrusion-based additive manufacturing remains underexplored. This study explores the impact of different base rubbers (NBR and EPDM) and curing agents (sulfur and peroxide) on processability and final part characteristics in material extrusion additive manufacturing applications. Under identical printing conditions, sulfur-cured NBR exhibits greater post-print shrinkage (12%) than sulfur-cured EPDM (7%). However, sulfur-cured NBR achieves a higher degree of adhesion between printed layers than sulfur-cured EPDM, as suggested by the % retention of the bulk materials' ultimate stress by the printed parts (84-100% and 51-62%, respectively). Additionally, a peroxide-cured NBR formulation was compared against the same sulfur-cured NBR formulation. Printed parts from the peroxide-cured NBR formulation showed higher shrinkage (16%) and lower % retention of the bulk materials' ultimate stress (26-33%) than the sulfur-cured NBR formulation. Additionally, the tensile behavior of all three rubber compounds was found to be strongly dependent on printing orientation, showing the anisotropic behavior typical of extrusion-based additive manufacturing. Sulfur-cured NBR showed the least anisotropy for stress at break (0.82) and strain at break (0.90), whereas peroxide-cured NBR showed the highest anisotropy in stress (0.74) and strain (0.82). The anisotropy ratios for sulfur-cured NBR and EPDM compounds were very similar for stress (0.82 vs. 0.82) and comparable for strain (0.90 vs. 0.87). Notably, the peroxide cure system provided almost twice as much available printing time as the sulfur cure system. This report on the effects of base rubber and curing agents on 3D printability and part properties provides a background to guide future efforts to design rubber compounds for 3D printing applications.